CN114180533B - Green regeneration method and device for octahydroanthraquinone in working solution for hydrogen peroxide production - Google Patents
Green regeneration method and device for octahydroanthraquinone in working solution for hydrogen peroxide production Download PDFInfo
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- 238000011069 regeneration method Methods 0.000 title claims abstract description 118
- GOOYDFBDQNFLQJ-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,9a,10a-decahydroanthracene-9,10-dione Chemical compound O=C1C2=CCCCC2C(=O)C2C1CCCC2 GOOYDFBDQNFLQJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000012224 working solution Substances 0.000 title claims abstract description 80
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 230000008929 regeneration Effects 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 21
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims description 30
- 230000000694 effects Effects 0.000 claims description 25
- 238000003860 storage Methods 0.000 claims description 23
- 238000000605 extraction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004581 coalescence Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- -1 alkali metal salt Chemical class 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 18
- 238000012546 transfer Methods 0.000 abstract description 11
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 6
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VDEBMALSPYBBET-UHFFFAOYSA-N 1,2,3,4,4a,5,9a,10a-octahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CCC2C(=O)C2C1CCCC2 VDEBMALSPYBBET-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AXHRXVXCOMMNLG-UHFFFAOYSA-N 1-hydroxy-10h-anthracen-9-one Chemical compound C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O AXHRXVXCOMMNLG-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- AEGIBGAOWQITBI-UHFFFAOYSA-N anthracene-9,10-dione benzene Chemical group C1=CC=CC=C1.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 AEGIBGAOWQITBI-UHFFFAOYSA-N 0.000 description 1
- WUOFAZKBVWWYER-UHFFFAOYSA-N anthracene-9,10-dione;hydrogen peroxide Chemical compound OO.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 WUOFAZKBVWWYER-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000007517 lewis acids Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of hydrogen peroxide production processes, and particularly relates to a green regeneration method of octahydroanthraquinone in working solution for hydrogen peroxide production, which comprises the following steps: under the action of a catalyst, the tetrahydroanthraquinone and the octahydroanthraquinone in the working solution are converted into anthraquinone and octahydroanthraquinone through hydrogen transfer and proton exchange chemical reaction, and then the generated octahydroanthraquinone is oxidized into octahydroanthraquinone through oxidation reaction; stage of regenerating octahydroanthraquinone: under the action of a catalyst, the octahydroanthraquinone in the working solution is converted into anthraquinone and octahydroanthraquinone through a hydrogen transfer process, and then the octahydroanthraquinone is converted into octahydroanthraquinone until the octahydroanthraquinone is converted into anthraquinone according to a regeneration target. The invention creatively adopts a chemical hydrogen transfer and chemical dehydrogenation process to convert the octahydroanthraquinone in the working solution into the effective anthraquinone to the maximum extent, and the regeneration conversion rate is 80-99%.
Description
Technical Field
The invention belongs to the technical field of hydrogen peroxide production processes, and particularly relates to a green regeneration method of octahydroanthraquinone in working solution for hydrogen peroxide production.
Background
The fluidized bed anthraquinone process hydrogen peroxide production process is an advanced hydrogen peroxide production process in the world at present, and compared with the domestic fixed bed process, the process has the advantages that the system working solution is fully acidic, the unit working solution productivity is about 13g/L, the energy consumption and the raw material consumption are low, the product quality is high, the occupied area of the device is small, and the safety performance is high. The hydrogenation reactor of the core reactor of the process is a fluidized bed, and the working solution is subjected to main reaction under the influence of the fluidization state in a tower and process control conditions because the palladium content of the catalyst in the system is higher by 0.5-5 percent: the hydrogenation reaction and the oxidation reaction simultaneously have a certain degree of side reaction, and the side reaction of the hydrogenation reaction is mainly reflected in the deep hydrogenolysis of anthraquinone benzene ring and carbonyl, and the by-product of the deep hydrogenolysis is as follows: hydroxyanthrone, hexahydroanthraquinone, octahydroanthraquinone, decahydroanthraquinone, anthrone (9-anthrone, 10-anthrone, anthrone dimer), oxidation by-products of working fluid: epoxy anthraquinones (tetrahydroepoxy anthraquinone, hexahydroepoxy anthraquinone, octahydroepoxy anthraquinone). The gradual accumulation of the series of byproducts along with the increase of the running time of the device can influence the physicochemical property of the working solution in the system, reduce the productivity of the working solution and influence the extraction effect, wherein the anthraphenone and the epoxy anthraquinone can be converted into effective anthraquinone by a regeneration mode, but the byproducts of deep hydrogenolysis: the byproducts such as hexahydroanthraquinone, octahydroanthraquinone and the like still have no effective regeneration mode at home and abroad at present, the octahydroanthraquinone is a byproduct which is easy to hydrogenate and difficult to oxidize, part of the octahydroanthraquinone exists in a system working solution in a form of octahydroanthraquinone, the part of the byproduct can cause partial high residual hydrogen efficiency of the system, only tetrahydroanthraquinone and isomeric tetrahydroanthraquinone can be oxidized in an oxidation tower, and the octahydroanthraquinone can only oxidize 3-15 percent, so that the oxidizing capacity is insufficient, the part of octahydroanthraquinone can not circulate in the system, the productivity of the device is reduced, the octahydroanthraquinone proportion in the working solution is increased cumulatively along with the increase of the circulation times of the working solution, and the working solution state is deteriorated: the viscosity is larger, the hydro-anthraquinone is easy to separate out, the surface tension is reduced, the density is increased, the burden of a filtering system is increased, the oil-water separation effect of an extraction tower is reduced, the working solution is higher with water and the raffinate hydrogen peroxide, and the continuous production of the device is difficult to maintain.
At present, no research on the mechanism of the regeneration of the octahydroanthraquinone at home and abroad is carried out, no effective regeneration method of the octahydroanthraquinone is carried out, but the content of the octahydroanthraquinone is monitored in the process operation and is balanced for a short time by frequently replacing clay and periodically replacing working solution, so that the consumption of clay, solvent and carrier anthraquinone is high, and a long-term accumulation device cannot continuously operate.
Disclosure of Invention
The invention aims to provide a green regeneration method of octahydroanthraquinone in working solution for hydrogen peroxide production, which is characterized in that the reaction mechanism and the reaction process are deeply researched, the intermediate products and the products are accurately qualitatively and quantitatively analyzed, a complete technological route is innovatively developed through a fully perfected laboratory small test, and industrial equipment is successfully applied to industrialization after pilot plant test.
The specific technical scheme of the invention is as follows:
the reaction mechanism history of octahydroanthraquinone regeneration is as follows: based on the principle of hydrogen transfer and proton exchange, the recycling regeneration of the octahydroanthraquinone is realized from the standpoint of chemical equilibrium, the regeneration process needs to go through 2 necessary stages, namely a regenerated tetrahydroanthraquinone stage and a regenerated octahydroanthraquinone stage, and the specific regeneration mechanism is as follows:
The first stage: under the action of a catalyst, the tetrahydroanthraquinone and the octahydroanthraquinone in the working solution are converted into anthraquinone and octahydroanthraquinone through hydrogen transfer and proton exchange chemical reaction, and the generated octahydroanthraquinone is oxidized into octahydroanthraquinone through oxidation reaction because the reaction is reversible, so that the regeneration reaction is ensured to be continuously carried out in the forward and reverse directions.
And a second stage: under the action of a catalyst, octahydroanthraquinone in the working solution is converted into anthraquinone and octahydroanthraquinone through a hydrogen transfer process, and the reversible reaction and parallel reaction exist in the reaction: simultaneously, the generated anthraquinone is subjected to hydrogen transfer to generate anthrahydroquinone, so that the octahydro anthraquinone is required to be converted into the octahydro anthraquinone until the octahydro anthraquinone is converted into the anthraquinone according to the regeneration target.
The specific chemical structural reaction formula is as follows:
The chemical reaction can be carried out at a higher rate under the catalysis of the catalyst, the oxide of alkali metal or alkaline earth metal in the S or P region, the composite oxide or the mixture of the oxide and the salt are selected as the catalyst through research, the regeneration reaction principle is Lewis acid reaction, the catalytic activity, the selectivity and the stability of the selected catalyst are verified through experiments, and the substances influencing the activity of the catalyst are defined: the ligand anions, the strong polar substances and the H 2 0, if the content of toxic substances is higher in the regeneration process, the catalyst is temporarily deactivated, the progress of side reactions to generate macromolecular polar substances is accelerated, the regeneration conversion rate is reduced, and the color of the regenerated working solution is deepened, so that the control of raw materials and operation conditions in the industrial conversion process is particularly important, and the industrial operation result shows that the conversion rate of octahydroanthraquinone is about 90%, and meanwhile, the cell configuration, the surface property, the pore channel structure, the acid center, the specific surface and the like of the catalyst are measured and compared by an advanced technical detection means SETM, XRD, BET, so that a metal oxide and composite oxide catalyst with lower preparation cost is successfully found under the conditions of ensuring higher catalytic activity, selectivity and efficiency, and industrial application is carried out on the device.
The catalyst is prepared from alkali metal salt, alkaline earth metal salt, noble metal oxide, ferrous metal (such as Fe, etc.), amphoteric metal (such as Al, etc.), and single or two or more of them as main components by making into solid particles.
The operating conditions of the industrial device of the octahydroanthraquinone are defined by laboratory small test and pilot scale up: the content (area percentage) of target substance octahydroanthraquinone is reduced from 4.2% to 0.25% (which can be adjusted up and down), a, the equilibrium conversion rate is 20% (ideal plug flow airspeed is less than 5h -1), and the working solution needs to be recycled for regeneration; b. the equilibrium conversion rate is 13 percent (the fluid continuous flow airspeed is less than or equal to 9), and the regeneration cycle times of the working solution are increased; c. the equilibrium conversion 10% (fluid continuous flow airspeed 1.0) is higher than the working fluid frequency and is related to the target. Different routes are selected according to the requirements of the working fluid of the device.
The invention also discloses a green regeneration device of the octahydroanthraquinone in the working solution for producing hydrogen peroxide, which comprises a fixed bed regeneration reactor, wherein a feed inlet of a distributor at the bottom of the fixed bed regeneration reactor is connected with a discharge port of a regeneration working solution heating storage tank through a pipeline, an inert gas inlet and a pressure gauge are arranged on the fixed bed regeneration reactor, a flow control valve is arranged at the feed inlet of the distributor, a circulating discharge port of the fixed bed regeneration reactor is connected with the feed inlet of the storage tank through a pipeline, a discharge port of the storage tank is connected with a feed inlet of a coalescence dewatering device through a pump, and a discharge port of the coalescence dewatering device is connected with the feed inlet of the regeneration working solution heating storage tank through a pipeline; the discharge port of the fixed bed regeneration reactor is connected with the feed port of the regeneration liquid storage tank through a pipeline, and the discharge port of the regeneration liquid storage tank is connected with the feed port of the oxidation tower through a pump; the discharge port of the oxidation tower is connected with the feed inlet of the extraction tower through a pipeline, the discharge port of the extraction tower is connected with the feed inlet of the coalescence water removing device through a pipeline, and the discharge port of the coalescence water removing device is connected with the feed inlet of the regeneration working solution heating storage tank through a pipeline. The discharge port of the oxidation tower is also connected with the feed inlet of the oxidation tower through a branch pipeline.
When the technological route is selected, the characteristics of the existing device are fully considered in combination with the regeneration reaction mechanism, the technical route of the industrial application of the octahydroanthraquinone recycling regeneration device based on the existing device is successfully designed by maximally utilizing the existing device equipment, the flow directions of different regeneration stages of materials are adjusted, and only part of bridging pipelines are needed to be added. The specific process technical route is as follows:
(1) And (3) step regeneration of the working solution: the method comprises the steps of using a fixed bed regeneration reactor, enabling a regeneration working solution to enter the regeneration reactor from a bottom distributor to carry out chemical regeneration of octahydroanthraquinone after being heated to a target temperature of 75-90 ℃, enabling the effect of regeneration reaction to be ensured, inhibiting side reaction and improving the reaction safety coefficient, enabling the regeneration reactor to react under the protection of inert gas, enabling the working solution to be in uniform contact with a catalyst to avoid channeling and bias flow phenomena, enabling the top pressure of the mass transfer efficiency reactor to be maintained at 100-120kPa, enabling a system to continuously operate, enabling the system to ensure the activity of the catalyst, requiring special dewatering and coalescing equipment, maintaining high-volume operation, enabling the water content of the working solution entering the regeneration reaction tower to be less than or equal to 3000ppm, enabling the working solution entering a storage tank after regeneration completion to enter a subsequent coalescing and dewatering system after being pressurized by a pump, enabling the working solution entering the regeneration reaction tower after water to exchange heat, recycling to carry out periodic regeneration, enabling the catalyst to enter a process route of a second stage to operate by GC periodically, monitoring the activity of the catalyst to be monitored by hydrogen effect when the content of the octahydroanthraquinone in the working solution is less than or equal to 0.25%, and enabling the activity of the catalyst to be periodically monitored by hydrogen effect, and if the hydrogen efficiency is increased to be less than or equal to 1.2g/L in 4 hours, and the activity is regarded as weak, and the catalyst is required.
(2) And (3) carrying out continuous oxidation extraction by a system: at this time, the regeneration reactor was cut out, and the pressure was maintained at 100kPa with an inert gas, and the completely converted octahydroanthraquinone working solution was continuously oxidized to ensure that the regeneration reaction in the next stage was performed in the forward reaction direction. And the regenerated liquid is pressurized by a pump from a regenerated liquid storage tank to 700-760kPa and enters an oxidation tower for oxidation, so that the same oxidation condition as that of an industrial device is ensured. In specific cases, the full analysis result of the discharged working solution of the oxidation tower is needed until the content of the octahydroanthraquinone is not continuously increased.
(3) And (3) continuously removing water from the system: after the system oxidation is completed, the octahydroanthraquinone and a small amount of hydroanthraquinone converted by the regeneration reactor are completely oxidized into octahydroanthraquinone and anthraquinone, and the generated low-concentration hydrogen peroxide is recovered after countercurrent extraction by the extraction tower, the working solution is required to be dehydrated by means of coalescence, vacuum and the like until the water content of the working solution in the system is less than or equal to 3000ppm, the oxidation reactor and the extraction tower are cut out, and the circulation operation and regeneration stage is continued until the octahydroanthraquinone is lower than the target content.
Advantageous effects
The invention discloses a green regeneration method of octahydroanthraquinone in working solution for hydrogen peroxide production, which breaks through the blank of the research of the octahydroanthraquinone regeneration principle at home and abroad in the industry by the reaction principle of the technical scheme, and is successfully verified by an industrial device. The method is a domestic first-class creator, can monitor the chemical regeneration process of the working fluid in time and ensures high-volume conversion of the octahydroanthraquinone.
The catalyst selected by the technical scheme is metal oxide and composite oxide with high activity and low cost, and the preparation process is simpler and can realize industrialized mass production.
The technical proposal has high technical advanced level and high running elasticity: the device can be independently built, the existing production device of the anthraquinone hydrogen peroxide fluidized bed or fixed bed can be utilized, only a specific process operation route is matched, the investment of fixed equipment is not needed, only the time and energy cost factors are considered, and the device is operated in series in stages on the premise of ensuring the activity, the selectivity, the stability and the high conversion rate of the catalyst to the maximum extent, so that the energy consumption and the time cost are reduced.
The technical scheme has mild process control conditions, the regeneration reaction temperature is medium-low temperature, the regeneration pressure is low pressure, the reaction conditions of the serial oxidation extraction technical route are mild, the high activity and long-service-life operation of the regenerated catalyst are ensured through an advanced physical secondary water removal process, and the process has high safety and stability.
The technical scheme has high resource conversion rate, and the device industrialized application shows that: the recovery rate of anthraquinone before and after regeneration is 85-98%.
Drawings
Fig. 1 is a schematic structural view of a regenerating device according to embodiment 2 of the present invention;
In the figure, 1: a fixed bed regeneration reactor; 2: a distributor; 3: a regenerated working fluid heating storage tank; 4: an inert gas inlet; 5: a pressure gauge; 6: a flow control valve; 7: a circulating discharge port; 8: a storage tank; 9: a pump; 10: a coalescing water removal device; 11: a discharge port; 12: a regeneration liquid storage tank; 13: an oxidation tower; 14: an extraction column; 15: a solenoid valve.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
The green regeneration method of octahydroanthraquinone in working solution for hydrogen peroxide production comprises two stages: the specific regeneration method comprises the following steps of:
(1) Regeneration of tetrahydroanthraquinone: under the action of a catalyst, the tetrahydroanthraquinone and the octahydroanthraquinone in the working solution are converted into anthraquinone and octahydroanthraquinone through hydrogen transfer and proton exchange chemical reaction, and then the generated octahydroanthraquinone is oxidized into octahydroanthraquinone through oxidation reaction;
(2) Stage of regenerating octahydroanthraquinone: under the action of a catalyst, the octahydroanthraquinone in the working solution is converted into anthraquinone and octahydroanthraquinone through a hydrogen transfer process, and then the octahydroanthraquinone is converted into octahydroanthraquinone until the octahydroanthraquinone is converted into anthraquinone according to a regeneration target.
The catalyst is one or a combination of more of alkali metal salt, alkaline earth metal salt, noble metal oxide, ferrous metal and amphoteric metal oxide, and is prepared into solid particles, and the use method is a fixed bed layer.
The chemical conversion conditions of the regeneration method are as follows: weight space velocity is less than 5h -1, conversion reaction temperature is less than 160 ℃, and conversion reaction pressure is 20-550kPa.
Example 2
As shown in fig. 1, a green regeneration device of octahydroanthraquinone in working solution for hydrogen peroxide production comprises a fixed bed regeneration reactor 1, wherein a feed inlet of a distributor 2 at the bottom of the fixed bed regeneration reactor is connected with a feed outlet of a regeneration working solution heating storage tank 3 through a pipeline, an inert gas inlet 4 and a pressure gauge 5 are arranged on the fixed bed regeneration reactor, a flow control valve 6 is arranged at the feed inlet of the distributor, a circulating feed outlet 7 of the fixed bed regeneration reactor is connected with a feed inlet of a storage tank 8 through a pipeline, a feed outlet of the storage tank is connected with a feed inlet of a coalescence dewatering device 10 through a pump 9, and a feed outlet of the coalescence dewatering device is connected with a feed inlet of the regeneration working solution heating storage tank 3 through a pipeline; the discharge port 11 of the fixed bed regeneration reactor is connected with the feed port of a regeneration liquid storage tank 12 through a pipeline, and the discharge port of the regeneration liquid storage tank is connected with the feed port of an oxidation tower 13 through a pump 9; the discharge gate of oxidation tower passes through the pipeline and is connected with the feed inlet of extraction tower 14, the discharge gate of extraction tower passes through the pipeline and is connected with the feed inlet of coalescence water trap 10, the discharge gate of coalescence water trap passes through the pipeline and is connected with the feed inlet of regeneration working solution heating storage tank 3. The discharge port of the oxidation tower 13 is also connected with the feed port of the oxidation tower through a branch pipeline.
Example 3
The green regeneration of the octahydroanthraquinone in the working solution for hydrogen peroxide production is carried out by using the regeneration device described in the embodiment 2, and the specific process technical route is as follows:
(1) And (3) step regeneration of the working solution: the method comprises the steps of using a fixed bed regeneration reactor, enabling a regeneration working solution to enter the regeneration reactor from a bottom distributor to carry out chemical regeneration of octahydroanthraquinone after being heated to a target temperature of 75-90 ℃, enabling the effect of regeneration reaction to be ensured, inhibiting side reaction and improving the reaction safety coefficient, enabling the regeneration reactor to react under the protection of inert gas, enabling the working solution to be in uniform contact with a catalyst to avoid channeling and bias flow phenomena, enabling the top pressure of the mass transfer efficiency reactor to be maintained at 100-120kPa, enabling a system to continuously operate, enabling the system to ensure the activity of the catalyst, requiring special dewatering and coalescing equipment, maintaining high-volume operation, enabling the water content of the working solution entering the regeneration reaction tower to be less than or equal to 3000ppm, enabling the working solution entering a storage tank after regeneration completion to enter a subsequent coalescing and dewatering system after being pressurized by a pump, enabling the working solution entering the regeneration reaction tower after water to exchange heat, recycling to carry out periodic regeneration, enabling the catalyst to enter a process route of a second stage to operate by GC periodically, monitoring the activity of the catalyst to be monitored by hydrogen effect when the content of the octahydroanthraquinone in the working solution is less than or equal to 0.25%, and enabling the activity of the catalyst to be periodically monitored by hydrogen effect, and if the hydrogen efficiency is increased to be less than or equal to 1.2g/L in 4 hours, and the activity is regarded as weak, and the catalyst is required.
(2) And (3) carrying out continuous oxidation extraction by a system: at this time, the regeneration reactor was cut out, and the pressure was maintained at 100kPa with an inert gas, and the completely converted octahydroanthraquinone working solution was continuously oxidized to ensure that the regeneration reaction in the next stage was performed in the forward reaction direction. And the regenerated liquid is pressurized by a pump from a regenerated liquid storage tank to 700-760kPa and enters an oxidation tower for oxidation, so that the same oxidation condition as that of an industrial device is ensured. Can circularly oxidize, and in particular, the full analysis result of the discharged working solution of the oxidation tower is needed until the content of the octahydroanthraquinone is no longer continuously increased.
(3) And (3) continuously removing water from the system: after the system oxidation is completed, the octahydroanthraquinone and a small amount of hydroanthraquinone converted by the regeneration reactor are completely oxidized into octahydroanthraquinone and anthraquinone, and the generated low-concentration hydrogen peroxide is recovered after countercurrent extraction by the extraction tower, the working solution is required to be dehydrated by means of coalescence, vacuum and the like until the water content of the working solution in the system is less than or equal to 3000ppm, the oxidation reactor and the extraction tower are cut out, and the circulation operation and regeneration stage is continued until the octahydroanthraquinone is lower than the target content.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (7)
1. The green regeneration method of the octahydroanthraquinone in the working solution for producing the hydrogen peroxide is characterized by comprising the following steps of:
(1) And (3) step regeneration of the working solution: the method comprises the steps of carrying out regeneration reaction by using a fixed bed regeneration reactor, enabling a regeneration working solution to enter the regeneration reactor from a bottom distributor to carry out chemical regeneration of octahydroanthraquinone after being heated to a target temperature of more than 75 ℃, enabling the regeneration reactor to react under the protection of inert gas, enabling the pressure at the top of the reactor to be maintained at 100-120kPa, enabling the space velocity of the working solution entering the regeneration reactor to be less than or equal to 8.5h -1, continuously running the system, enabling the working solution after regeneration to enter a storage tank to enter a subsequent coalescence dewatering device after being pressurized by a pump, continuously entering the regeneration reactor after dewatering and heat exchange, ensuring that the water content of the working solution entering the regeneration reactor is less than or equal to 3000ppm, recycling the working solution for periodic regeneration, periodically monitoring the regeneration effect through GC until the octahydroanthraquinone content in the working solution is less than or equal to 0.25%, periodically monitoring the catalyst activity through hydrogen effect during the period, and regarding the catalyst activity as weak when the hydrogen efficiency is increased by less than or equal to 1.2g/L within 4 hours, and replacing the catalyst;
(2) And (3) carrying out continuous oxidation extraction by a system: when the content of octahydroanthraquinone in the working solution is less than or equal to 0.25%, cutting out the regeneration reactor, maintaining the pressure by using inert gas for 100kPa, enabling the working solution to enter a regeneration solution storage tank, pressurizing the completely converted octahydroanthraquinone working solution by a pump for 700-760kPa, and then entering an oxidation tower for continuous oxidation so as to ensure that the regeneration reaction of the next stage is carried out towards the positive reaction direction;
(3) And (3) continuously removing water from the system: after the system is oxidized, the octahydroanthraquinone converted by the regeneration reactor is completely oxidized into octahydroanthraquinone and anthraquinone, and the generated low-concentration hydrogen peroxide is recovered after countercurrent extraction by the extraction tower, the working solution is required to be dehydrated by coalescence and vacuum until the water content of the working solution in the system is less than or equal to 3000ppm, the system is stopped, and the oxidation reactor and the extraction tower are cut out to continue to circularly run the regeneration stage until the octahydroanthraquinone is lower than the target content.
2. The method for green regeneration of octahydroanthraquinone in a working solution for hydrogen peroxide production according to claim 1, wherein the catalyst is one or a combination of more of alkali metal salt, alkaline earth metal salt, noble metal oxide, ferrous metal and amphoteric metal oxide.
3. The green regeneration method of octahydroanthraquinone in a working solution for hydrogen peroxide production according to claim 2, wherein the catalyst is prepared into solid particles, and the application method is a fixed bed layer or a suspension bed.
4. The green regeneration method of octahydroanthraquinone in a working solution for hydrogen peroxide production according to claim 1, wherein the chemical conversion conditions of the regeneration method are as follows: weight space velocity is less than 5h -1, conversion reaction temperature is less than 160 ℃, and conversion reaction pressure is 20-550kPa.
5. The method for green regeneration of octahydroanthraquinone in a working solution for hydrogen peroxide production according to claim 1, wherein the catalyst in the step (1) is added in an amount of >1% in terms of catalyst-to-oil ratio.
6. The method for green regeneration of octahydroanthraquinone in a working solution for hydrogen peroxide production according to claim 1, wherein the catalyst in the step (2) is added in an amount of >0.5% in terms of catalyst-to-oil ratio.
7. The green regeneration method of octahydroanthraquinone in a working solution for hydrogen peroxide production according to claim 1, wherein the working solution in the step (2) needs to be circularly oxidized until the octahydroanthraquinone content in the working solution is no longer continuously increased.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769092A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for hydrogen peroxide production through anthraquinone method and preparation method thereof |
| CN106540685A (en) * | 2015-09-17 | 2017-03-29 | 中国石油化工股份有限公司 | The method of the renovation process and production hydrogen peroxide of catalyst and preparation method and purposes and hydrogen peroxide working solution produced by anthraquinone process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769092A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for hydrogen peroxide production through anthraquinone method and preparation method thereof |
| CN106540685A (en) * | 2015-09-17 | 2017-03-29 | 中国石油化工股份有限公司 | The method of the renovation process and production hydrogen peroxide of catalyst and preparation method and purposes and hydrogen peroxide working solution produced by anthraquinone process |
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